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US11753430B2 - Method of making cobalt compounds for feed supplements - Google Patents

Method of making cobalt compounds for feed supplements Download PDF

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Publication number
US11753430B2
US11753430B2 US17/307,095 US202117307095A US11753430B2 US 11753430 B2 US11753430 B2 US 11753430B2 US 202117307095 A US202117307095 A US 202117307095A US 11753430 B2 US11753430 B2 US 11753430B2
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mixture
acid
making
cobalt compound
set forth
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US20210380621A1 (en
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Marvin B. DeTar
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Vitalix Inc
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Vitalix Inc
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06Cobalt compounds
    • C07F15/065Cobalt compounds without a metal-carbon linkage
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D1/00Evaporating
    • B01D1/06Evaporators with vertical tubes
    • B01D1/065Evaporators with vertical tubes by film evaporating
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/105Aliphatic or alicyclic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/10Feeding-stuffs specially adapted for particular animals for ruminants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D1/00Evaporating
    • B01D1/22Evaporating by bringing a thin layer of the liquid into contact with a heated surface
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41Preparation of salts of carboxylic acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • B01D9/0004Crystallisation cooling by heat exchange
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • B01D9/004Fractional crystallisation; Fractionating or rectifying columns
    • B01D9/0045Washing of crystals, e.g. in wash columns
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D9/00Crystallisation
    • B01D9/0081Use of vibrations, e.g. ultrasound

Definitions

  • the present invention relates to feed supplements, and more particularly to a method of making cobalt compounds for feed supplements.
  • Cobalt is a component of Vitamin B 12 .
  • Vitamin B 12 is produced in ruminant animals by microorganisms in the rumen.
  • Cobalt can be provided in feed supplements for livestock, such as cattle, goats and sheep, to prevent Vitamin B 12 deficiency.
  • cobalt compounds cannot be used in feed supplements. Some cobalt compounds, such as cobalt metal and dicobalt carbonyl are toxic. Cobalt carbonate has been used as a feed supplement for many years, but a significant portion of it is not taken up easily by many of the microorganisms in the rumen. Cobalt chloride releases hydrogen chloride which can deactivate enzymes and is an irritant on the tongue. Cobalt oxide and cobalt hydroxide are very insoluble at physiological temperatures and are not useful in feed supplements.
  • Cobalt lactate, cobalt propionate, cobalt gluconate and cobalt heptogluconate can be used in feed supplements.
  • the bioavailability of these compounds can be improved by increasing the relative surface area.
  • Prior known methods for producing these compounds have required high temperatures, high magnetic fields or grinding the product of the chemical reaction.
  • a method of making a cobalt compound for feed supplements includes the steps of dissolving cobalt acetate tetrahydrate in water at a selected temperature to form a mixture, adding a selected acid to the mixture, sonicating the mixture for a selected time, removing acetic acid from the mixture, and separating crystals of the cobalt compound from the mixture.
  • the method may include the step of stirring or rotating the mixture during the step of sonicating.
  • the step of separating may also include the substep of precipitating the crystals from the mixture by cooling the mixture.
  • a method of making a cobalt compound for feed supplements includes the steps of dissolving cobalt acetate tetrahydrate in water at a selected temperature to form a mixture, adding a selected acid to the mixture, sonicating the mixture for a selected time, removing acetic acid from the mixture, and separating crystals of the cobalt compound from the mixture.
  • the selected acid can be any carboxylic acid.
  • lactic, propionic, gluconic and heptogloconic are used to produce cobalt lactate, cobalt propionate, cobalt gluconate and cobalt heptogluconate, respectively.
  • the cobalt acetate tetrahydrate is dissolved in a minimum of water at between 55° C. and 70° C.
  • the subsequent steps are modified depending on the pKa and boiling point of the selected acid.
  • Acetic acid has a pKa of 4.75.
  • the step of adding includes dissolving the selected acid in a minimum of water at 55° C. and adding the selected acid so that the mole ratio of acid to cobalt is preferably 2.02 or more, more preferably 2.13 or more and most preferably 2.25 or more.
  • the method may include the step of stirring the mixture during the step of sonicating.
  • the step of sonicating includes sonicating the mixture at about 0.25 watts/cm 2 at 20-55 KHz, or sufficient power that standing waves are clearly visible, for about one hour.
  • the step of separating includes the substep of reducing the temperature to 17° C. or below, during the step of sonicating, to precipitate the crystals from the mixture.
  • the step of separating can also include the substeps of filtering, washing with cold water to remove acetic acid and drying the crystals.
  • the step of removing acetic acid from the mixture can include sparging with a wet stream of nitrogen at 55° C. or subjecting the mixture to thin film evaporation of acetic acid under reduced pressure or both.
  • the step of adding includes adding the selected acid so that the mole ratio of acid to cobalt is 2.25 or more.
  • the method can include the step of rapidly rotating the mixture during the step of sonicating.
  • the step of sonicating includes sonicating the mixture at 55° C. at about 0.3 watts/cm 2 at 20-55 KHz.
  • the step of removing acetic acid from the mixture can include subjecting the mixture to thin film evaporation of acetic acid under reduced pressure.
  • the step of adding includes adding the propionic acid so that the mole ratio of acid to cobalt is 3.0 or more.
  • the method includes the step of rapidly rotating the mixture during the step of sonicating.
  • the step of sonicating includes sonicating the mixture at 55° C. and at about 0.4 watts/cm 2 at 20-55 KHz.
  • the step of removing acetic acid from the mixture includes slowly evacuating acetic acid at reduced pressure while adding 95% propionic acid as needed.
  • the azeotrope of water and propionic acid boils at about 99° C. and acetic acid boils at about 117° C., at atmospheric pressure.
  • Propionic acid boils at about 42° C. at 20 mm Hg, and acetic acid boils at about 17° C. at 10 mm Hg.
  • the step of separating can also include vacuum drying the mixture. The temperature is kept below about 70° C. to prevent formation of sticky cobalt hydroxides.
  • the step of removing acetic acid can include blending the mixture into basic inorganic materials that then form acetate salts, primarily with calcium, magnesium, potassium or sodium ions.
  • the step of separating can include containing the crystals in a slurry, suspension, or gel.
  • the method can also include a step of forming a premix, including the substeps of adding, after the step of dissolving, gluconic acid to provide an almost 1:1 premix mixture of cobalt acetate and cobalt gluconate compounds, and then sonicating the premix mixture.
  • the premix remained in solution at 15° C. for over ten days.
  • additional gluconic acid 1.1 eq of total gluconic acid to acetic acid
  • Sonicating the mixture with ultrasonic frequencies causes pressure waves where molecules are jostled apart, promoting both the exchange of acetic acid to the selected acid and promoting formation of fine crystals.
  • the method produces cobalt compounds for feed supplements without requiring high temperatures, high magnetic fields or grinding the product of the chemical reaction.
  • the method produces fine crystals with a relatively high surface area and high bioavailability for the microorganisms in the rumen.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Birds (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method of making a cobalt compound for feed supplements includes the steps of dissolving cobalt acetate tetrahydrate in water to form a mixture, adding an acid to the mixture, sonicating the mixture for a selected time, removing acetic acid from the mixture, and separating crystals of the cobalt compound from the mixture.

Description

TECHNICAL FIELD
The present invention relates to feed supplements, and more particularly to a method of making cobalt compounds for feed supplements.
BACKGROUND ART
Cobalt is a component of Vitamin B12. Vitamin B12 is produced in ruminant animals by microorganisms in the rumen. Cobalt can be provided in feed supplements for livestock, such as cattle, goats and sheep, to prevent Vitamin B12 deficiency.
Most cobalt compounds cannot be used in feed supplements. Some cobalt compounds, such as cobalt metal and dicobalt carbonyl are toxic. Cobalt carbonate has been used as a feed supplement for many years, but a significant portion of it is not taken up easily by many of the microorganisms in the rumen. Cobalt chloride releases hydrogen chloride which can deactivate enzymes and is an irritant on the tongue. Cobalt oxide and cobalt hydroxide are very insoluble at physiological temperatures and are not useful in feed supplements.
Cobalt lactate, cobalt propionate, cobalt gluconate and cobalt heptogluconate can be used in feed supplements. The bioavailability of these compounds can be improved by increasing the relative surface area. Prior known methods for producing these compounds have required high temperatures, high magnetic fields or grinding the product of the chemical reaction.
DISCLOSURE OF THE INVENTION
A method of making a cobalt compound for feed supplements includes the steps of dissolving cobalt acetate tetrahydrate in water at a selected temperature to form a mixture, adding a selected acid to the mixture, sonicating the mixture for a selected time, removing acetic acid from the mixture, and separating crystals of the cobalt compound from the mixture. The method may include the step of stirring or rotating the mixture during the step of sonicating. The step of separating may also include the substep of precipitating the crystals from the mixture by cooling the mixture.
BRIEF DESCRIPTION OF THE DRAWINGS
Details of this invention are described in connection with the accompanying drawings that bear similar reference numerals in which:
No figures.
DETAILED DESCRIPTION OF THE INVENTION
A method of making a cobalt compound for feed supplements, embodying features of the present invention, includes the steps of dissolving cobalt acetate tetrahydrate in water at a selected temperature to form a mixture, adding a selected acid to the mixture, sonicating the mixture for a selected time, removing acetic acid from the mixture, and separating crystals of the cobalt compound from the mixture.
The selected acid can be any carboxylic acid. For feed supplements, lactic, propionic, gluconic and heptogloconic are used to produce cobalt lactate, cobalt propionate, cobalt gluconate and cobalt heptogluconate, respectively.
In the step of dissolving, the cobalt acetate tetrahydrate is dissolved in a minimum of water at between 55° C. and 70° C. The subsequent steps are modified depending on the pKa and boiling point of the selected acid. Acetic acid has a pKa of 4.75.
For acids such as lactic acid, citric acid, erythorbic acid and acids in general possessing a pKa lower by about 0.05 units than acetic acid, the step of adding includes dissolving the selected acid in a minimum of water at 55° C. and adding the selected acid so that the mole ratio of acid to cobalt is preferably 2.02 or more, more preferably 2.13 or more and most preferably 2.25 or more. After the step of adding, the method may include the step of stirring the mixture during the step of sonicating. The step of sonicating includes sonicating the mixture at about 0.25 watts/cm2 at 20-55 KHz, or sufficient power that standing waves are clearly visible, for about one hour. The step of separating includes the substep of reducing the temperature to 17° C. or below, during the step of sonicating, to precipitate the crystals from the mixture. The step of separating can also include the substeps of filtering, washing with cold water to remove acetic acid and drying the crystals. The step of removing acetic acid from the mixture can include sparging with a wet stream of nitrogen at 55° C. or subjecting the mixture to thin film evaporation of acetic acid under reduced pressure or both.
For acids such as butyric, isobutyric, valeric, isovaleric and a variety of higher aliphatic acids and oleic, linolenic and linoleic acids, and acids in general possessing a pKa about equal to or higher than that of acetic acid, the step of adding includes adding the selected acid so that the mole ratio of acid to cobalt is 2.25 or more. The method can include the step of rapidly rotating the mixture during the step of sonicating. The step of sonicating includes sonicating the mixture at 55° C. at about 0.3 watts/cm2 at 20-55 KHz. The step of removing acetic acid from the mixture can include subjecting the mixture to thin film evaporation of acetic acid under reduced pressure.
For propionic acid the mixture is kept below about 70° C. The step of adding includes adding the propionic acid so that the mole ratio of acid to cobalt is 3.0 or more. The method includes the step of rapidly rotating the mixture during the step of sonicating. The step of sonicating includes sonicating the mixture at 55° C. and at about 0.4 watts/cm2 at 20-55 KHz. The step of removing acetic acid from the mixture includes slowly evacuating acetic acid at reduced pressure while adding 95% propionic acid as needed. The azeotrope of water and propionic acid boils at about 99° C. and acetic acid boils at about 117° C., at atmospheric pressure. Propionic acid boils at about 42° C. at 20 mm Hg, and acetic acid boils at about 17° C. at 10 mm Hg. The step of separating can also include vacuum drying the mixture. The temperature is kept below about 70° C. to prevent formation of sticky cobalt hydroxides.
The step of removing acetic acid can include blending the mixture into basic inorganic materials that then form acetate salts, primarily with calcium, magnesium, potassium or sodium ions. The step of separating can include containing the crystals in a slurry, suspension, or gel.
The method can also include a step of forming a premix, including the substeps of adding, after the step of dissolving, gluconic acid to provide an almost 1:1 premix mixture of cobalt acetate and cobalt gluconate compounds, and then sonicating the premix mixture. The premix remained in solution at 15° C. for over ten days. When additional gluconic acid (1.1 eq of total gluconic acid to acetic acid) was added, and gently mixed, within a half hour precipitation of very fine cobalt gluconate crystals occurred. This indicates that with the very low levels of water employed, this inorganic mixture retained a memory of its sonication. Without sonication, the cobalt gluconate crystals that formed exhibited less than 20 times the surface area observed with sonication.
Sonicating the mixture with ultrasonic frequencies causes pressure waves where molecules are jostled apart, promoting both the exchange of acetic acid to the selected acid and promoting formation of fine crystals. The method produces cobalt compounds for feed supplements without requiring high temperatures, high magnetic fields or grinding the product of the chemical reaction. The method produces fine crystals with a relatively high surface area and high bioavailability for the microorganisms in the rumen.
All of the ingredients have been designed to be reused. The acetic acid removed from the mixture can be reused. After the step of separating crystals of the cobalt compound from the mixture, the remaining mixture of cobalt compounds and the heavier carbon acids can be recycled into subsequent batches.
Although the present invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made by way of example and that changes in details of structure may be made without departing from the spirit thereof.

Claims (20)

What is claimed is:
1. A method of making a cobalt compound for feed supplements comprising the steps of:
dissolving cobalt acetate tetrahydrate in a minimum of water at between 55° C. and 70° C. to form a mixture,
adding a selected acid to said mixture,
sonicating said mixture for a selected time,
removing acetic acid from said mixture, and
separating crystals of said cobalt compound from said mixture.
2. The method of making a cobalt compound as set forth in claim 1 wherein said selected acid is a carboxylic acid.
3. The method of making a cobalt compound as set forth in claim 1 wherein said selected acid is chosen from the group consisting of lactic acid, propionic acid, gluconic acid and heptogloconic acid.
4. The method of making a cobalt compound as set forth in claim 1 wherein said step of adding, for acids possessing a pKa lower by about 0.05 units than acetic acid, includes dissolving said selected acid in a minimum of water at 55° C. and adding said selected acid so that the mole ratio of acid to cobalt is more than 2.25.
5. The method of making a cobalt compound as set forth in claim 4 including the step of stirring said mixture during said step of sonicating.
6. The method of making a cobalt compound as set forth in claim 5 wherein said step of sonicating includes sonicating said mixture at about 0.25 watts/cm2 at 20-55 KHz for about one hour at a power setting sufficient to provide standing waves at 20-55 KHz for about one hour.
7. The method of making a cobalt compound as set forth in claim 6 wherein said step of separating includes the substep of cooling said mixture, during said step of sonicating, to precipitate said crystals from said mixture.
8. The method of making a cobalt compound as set forth in claim 7 wherein said substep of cooling includes reducing the temperature to below 17° C.
9. The method of making a cobalt compound as set forth in claim 8 wherein said step of separating includes the substeps of filtering, washing with cold water and drying said crystals.
10. The method of making a cobalt compound as set forth in claim 1 wherein said step of adding, for acids possessing a pKa higher than acetic acid, includes adding the selected acid so that the mole ratio of acid to cobalt is more than 2.25.
11. The method of making a cobalt compound as set forth in claim 10 including the step of rapidly rotating said mixture during said step of sonicating.
12. The method of making a cobalt compound as set forth in claim 11 wherein said step of sonicating includes sonicating said mixture at 55° C. at about 0.3 watts/cm2 at 20-55 KHz.
13. The method of making a cobalt compound as set forth in claim 12 wherein said step of removing acetic acid from said mixture includes subjecting said mixture to thin film evaporation of acetic acid under reduced pressure.
14. The method of making a cobalt compound as set forth in claim 1 wherein said step of adding, for propionic acid, includes adding said selected acid so that the mole ratio of acid to cobalt is more than 3.0.
15. The method of making a cobalt compound as set forth in claim 14 including the step of rapidly rotating said mixture during said step of sonicating.
16. The method of making a cobalt compound as set forth in claim 15 wherein said step of sonicating includes sonicating the mixture at 55° C. at about 0.4 watts/cm2 at 20-55 KHz.
17. The method of making a cobalt compound as set forth in claim 16 wherein said step of removing acetic acid from said mixture includes slowly evacuating acetic acid at reduced pressure while adding 95% propionic acid as needed.
18. The method of making a cobalt compound as set forth in claim 1 wherein said step of removing acetic acid includes blending said mixture into basic inorganic materials that then form acetate salts.
19. The method of making a cobalt compound as set forth in claim 1 including the step of forming a premix, including the substeps of adding, after said step of dissolving, gluconic acid to provide an almost 1:1 premix mixture of cobalt acetate and cobalt gluconate compounds, and then sonicating said premix mixture.
20. A method of making a cobalt compound for feed supplements comprising the steps of:
dissolving cobalt acetate tetrahydrate in a minimum of water at between 55° C. and 70° C. to form a mixture,
adding a selected acid to said mixture, wherein said selected acid is chosen from the group consisting of lactic acid, propionic acid, gluconic acid and heptogloconic acid,
sonicating said mixture for a selected time,
removing acetic acid from said mixture, and
separating crystals of said cobalt compound from said mixture, including the substeps of cooling said mixture, during said step of sonicating, to precipitate said crystals from said mixture, filtering said crystals, washing said crystals with cold water and drying said crystals.
US17/307,095 2020-06-03 2021-05-04 Method of making cobalt compounds for feed supplements Active US11753430B2 (en)

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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3133942A (en) 1960-12-03 1964-05-19 Basf Ag Production of metal salts of organic acids
US3198635A (en) 1964-04-17 1965-08-03 Feed Service Corp Nutrient compositions and process for preparing same
US4009263A (en) 1974-02-15 1977-02-22 Shafer Laverne Energized cobalt-containing animal feed
US4060535A (en) 1976-08-31 1977-11-29 Tenneco Chemicals, Inc. Process for the production of metal salts of organic acids
USRE32909E (en) 1980-10-07 1989-04-18 Biosystems Research Inc. Metal oxycarboxylates and method of making same
US5591878A (en) 1995-09-19 1997-01-07 Kemin Industries, Inc. Catalyzed process for producing metal carboxylates for use as animal feed supplements
US5622739A (en) 1995-06-06 1997-04-22 K.E.S. Associates Feed block with improved mineral delivery
US5707679A (en) 1994-09-30 1998-01-13 Kemin Industries, Inc. Metal propionates for use as animal feed supplements
US5795615A (en) 1994-09-30 1998-08-18 Kemin Industries, Inc. Process for producing metal carboxylates for use as animal feed supplements
US7495117B2 (en) 2006-08-04 2009-02-24 Kemin Industries, Inc. Metal carboxylate salts
US8182573B2 (en) 2005-09-06 2012-05-22 ETH Zürich Methods and devices for flame spray pyrolysis
US8575212B2 (en) 2009-12-22 2013-11-05 Ralco Nutrition, Inc. Organically chelated mineral compositions and methods thereof
US9663438B2 (en) 2015-09-04 2017-05-30 Nutech Biosciences, Inc. Process for forming chromium propionate as an agricultural feed additive
US10265340B2 (en) 2012-02-22 2019-04-23 Kemin Industries, Inc. Animal feed compositions and methods of using the same
US20210015120A1 (en) * 2019-07-16 2021-01-21 Ralco Nutrition, Inc. Feed compositions

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3133942A (en) 1960-12-03 1964-05-19 Basf Ag Production of metal salts of organic acids
US3198635A (en) 1964-04-17 1965-08-03 Feed Service Corp Nutrient compositions and process for preparing same
US4009263A (en) 1974-02-15 1977-02-22 Shafer Laverne Energized cobalt-containing animal feed
US4060535A (en) 1976-08-31 1977-11-29 Tenneco Chemicals, Inc. Process for the production of metal salts of organic acids
USRE32909E (en) 1980-10-07 1989-04-18 Biosystems Research Inc. Metal oxycarboxylates and method of making same
US5707679A (en) 1994-09-30 1998-01-13 Kemin Industries, Inc. Metal propionates for use as animal feed supplements
US5795615A (en) 1994-09-30 1998-08-18 Kemin Industries, Inc. Process for producing metal carboxylates for use as animal feed supplements
US5622739A (en) 1995-06-06 1997-04-22 K.E.S. Associates Feed block with improved mineral delivery
US5591878A (en) 1995-09-19 1997-01-07 Kemin Industries, Inc. Catalyzed process for producing metal carboxylates for use as animal feed supplements
US8182573B2 (en) 2005-09-06 2012-05-22 ETH Zürich Methods and devices for flame spray pyrolysis
US7495117B2 (en) 2006-08-04 2009-02-24 Kemin Industries, Inc. Metal carboxylate salts
US8575212B2 (en) 2009-12-22 2013-11-05 Ralco Nutrition, Inc. Organically chelated mineral compositions and methods thereof
US10265340B2 (en) 2012-02-22 2019-04-23 Kemin Industries, Inc. Animal feed compositions and methods of using the same
US9663438B2 (en) 2015-09-04 2017-05-30 Nutech Biosciences, Inc. Process for forming chromium propionate as an agricultural feed additive
US20210015120A1 (en) * 2019-07-16 2021-01-21 Ralco Nutrition, Inc. Feed compositions

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